1. Field of the Invention
The present invention relates to the art of packaging using multi-layer films, and, in particular, to a new composite multi-layer film for providing hermetic seals to multi-layer film packages.
2. Description of the Prior Art
Packaging technology has over the years required the development of many disciplines. Currently, packaging technologies integrate elements of engineering, chemistry, food science, metallurgy, and other technologies in order to provide the consumer fresh food product. In those cases where packages are prepared from multi-layer film, it is desirable to be able to provide a hermetic seal, i.e., a seal which does not permit passage of gas such as air.
In recent years, containers produced out of multiple-layer flexible film, such as bags and pouches, predominate the marketplace. In order to utilize continuous multiple-layer flexible film, the industry generally employs form/fill/seal packaging techniques. The type of product packaged dictates whether or not the technique will include horizontal form/fill/seal packaging (HFFS) or vertical form/fill/seal packaging (VFFS).
It is important for the packaging artisan to be able to select a multi-layer film having optimum barrier properties for storage of the food items and be confident of providing a high quality seal using high speed packaging apparatus. For example, it is known that stereoregular polypropylene, e.g., oriented polypropylene, is quite useful in the manufacture of packages from flexible films. Using oriented polypropylene as a core layer, additional layers in the way of coatings, co-extrusions, laminations, and combinations thereof are added to improve barrier properties of the film. In certain cases, films can be prepared which exclude moisture and oxygen, but permit the passage of light. In other cases, it is also important to prevent light from passing through the film barrier. Barrier properties can also be modified and/or enhanced by treatments such as heat and flame treatment, electrostatic discharge, chemical treatments, halogen treatment, ultraviolet light, and combinations thereof.
A primary concern for designing multiple-layer films for packaging is to ensure they can be processed on high speed form/fill seal machinery. Form/fill/seal package apparatus operates by unwinding continuous film from bulk film rolls, followed by forming pouches therefrom, filling the pouches, and finally, sealing the pouch closed. Thus, the film must have sufficient flexibility to undergo machine folding from a flat orientation to a folded condition, and be subjected to a sealing function which is part of high-speed packaging apparatus. In selecting the optimum multi-layer film for its barrier properties, high-speed unrolling and folding are the primary concern. An additional, and very important aspect of the packaging process, however, is the ability to effectively seal the pouch after it is filled with the product.
High-speed horizontal and vertical form/fill/seal apparatus include sealing functions at various stages of the packaging process. In a horizontal form/fill/seal apparatus, individual pouches are formed by folding the multi-layer film in half followed by providing vertical seals along the length of the folded web and separating the pouches along the seals formed by vertical sealing. (Optionally, the bottoms of the pouches can also be sealed). After the pouch thusly formed is filled, the top of the pouch is sealed.
Similarly, in vertical form/fill/seal apparatus, the continuous web is formed around a tube and the web is immediately joined together by a longitudinal sealing jaw as either a lap seal or a fin seal. Lap seals and fin seals are depicted in U.S. Pat. Nos. 5,888,648, 5,888,648 is incorporated herein by reference in its entirety.
A second sealing function is present in a VFFS configuration which consists of a combination top- and bottom-sealing section (with a bag cut-off device in between). The top-sealing portion seals the bottom of an empty bag suspended from the bag forming tube while the bottom portion seals the top of a filled bag.
In order, therefore, to provide high-barrier multi-layer film with hermetic seals, several factors must be considered. It is important to provide a sealing capability at as low a temperature as possible in order to retain, among other things, stereoregularity imposed during orientation, little or no film shrinkage, retention of film and/or chemical additive properties, and highly consistent quality sealing capabilities. Furthermore, the film must have surface characteristics which permit it to be readily used on high-speed machinery. For example, the coefficient of friction must be such that it can be readily unrolled from a high volume roll of film and passed through the packaging machinery. Undesirable sticking or friction characteristics can cause bag imperfections and interruption of high-speed processing. Moreover, seals formed during process must have good seal strength.
More recently, the packaging artisan has been concerned with the ability to provide quality seals which preserve the freshness of the contents while providing the consumer with an easily openable and reclosable container. Innovations to date have been primarily concerned with the components of the seal material.
U.S. Pat. No. 3,202,528 describes an oriented polypropylene film having an adherent heat-sealable coating which includes a material from the group consisting of copolymers of vinylidene chloride and acrylonitrile, copolymers of vinyl chloride with vinyl acetate, chlorinated rubbers, nitrocellulose and polyamide which melts below 160xc2x0 C. and an acidic material provided in an amount of about 20 to about 60% by weight of the film forming material. This adhesive is coated and dried on the film. U.S. Pat. No. 3,202,528 is incorporated herein by reference in its entirety.
U.S. Pat. No. 4,020,228 describes a gel composition which provides a heat sealable surface to polyolefinic materials or cellulosic sheet materials. U.S. Pat. No. 4,121,956 discloses an ionomer adhesive adhered to an outer ionomeric surface of package wrapping for attachment of labels. U.S. Pat. No. 4,020,228 is incorporated herein by reference in its entirety.
U.S. Pat. No. 4,218,510 discloses a heat-sealable multi-layer film having a polyester layer chemically interfacially bonded to a polyolefinic layer which contains 250 to 750 parts per million of a fatty acid amide. U.S. Pat. No. 4,218,510 is incorporated herein by reference in its entirety.
U.S. Pat. No. 4,292,882 discloses an oriented heat-sealable anti-static polypropylene film manufactured by applying to a surface of a base polypropylene film a heat-sealable olefinic polymer containing between 0.2 and 10% by weight of an anionic hydrocarbyl sulfonate. Andrews, et al. also provide that a slip agent can be incorporated for ease of handling. U.S. Pat. No. 4,292,882 is incorporated herein by reference in its entirety.
U.S. Pat. No. 4,389,450 describes a multi-layer packaging film in which the outer polymeric layers cooperate to provide a relatively constant coefficient of friction differential. This enhances the ability to use the film in high speed processing to form fin seal and lap seals. U.S. Pat. No. 4,389,450 is incorporated herein by reference in its entirety.
U.S. Pat. No. 5,049,436 discloses a multi-layer film which is hermetically heat sealable over a broad temperature range. This patent describes a heat-sealable layer which includes an ethylene-propylene copolymer and/or an ethylene-propylene-butene terpolymer with an inorganic anti-block agent and a fatty acid amide. U.S. Pat. No. 5,049,436 is incorporated herein by reference in its entirety.
U.S. Pat. 5,376,437 describes a three-layer, heat sealable film having a base layer of biaxially oriented, crystalline polypropylene, a cushion layer of an olefin polymer lower in melting point than the base layer, and a heat-sealable layer of an olefin polymer. The various layers of this film have particular degrees of surface orientation. U.S. Pat. No. 5,376,437 is incorporated herein by reference in its entirety.
U.S. Pat. No. 5,527,608 describes a biaxially oriented heat sealable multilayer film which has a core substrate of a polyolefin homopolymer. On one surface of the core substrate is a layer of a block copolymer of ethylene and propylene having a melt flow ratio (MFR) of 1 to 10. A high density polyethylene layer may be placed on the other surface of the core substrate, and a heat sealable layer may be placed over the block copolymer layer. The heat sealable layer may be formed from a terpolymer of ethylene, propylene and butene-1, a random copolymer of ethylene and propylene, a random copolymer of propylene and butene-1 or blends thereof. U.S. Pat. No. 5,527,608 is incorporated herein by reference in its entirety.
U.S. Pat. No. 5,888,648 describes a multi-layer, hermetically sealable film. The main film substrate may be oriented polypropylene, optionally having a layer of high density polyethylene on one surface of the polypropylene. On the surface of the polypropylene opposite the high density polyethylene layer is an intermediate layer of polyethylene homo-, co- and terpolymers, amorphous nylon, ionomers or mixtures thereof. A preferred polymer in the intermediate layer is low density polyethylene. On the exterior surface of the intermediate layer is a sealing layer of, e.g., polyethylene homo-, co- and terpolymers, amorphous nylon, ionomers or mixtures thereof. U.S. Pat. No. 5,888,648 is incorporated herein by reference in its entirety.
U.S. Pat. No. 6,058,680 describes an apparatus and method for forming a hermetically sealed package for a slice of a food item. A web of thermoplastic material is first formed into a tubular arrangement with a hermetic longitudinal seal. To form the tubular arrangement, means are provided for folding a continuous web of thermoplastic material into V-folded condition and for continuously forming a hermetic seal along the open longitudinal edge of the V-folded web. The hermetic seal is formed between the inner surfaces of the front and rear faces of the web to define a tubular web member. The food item which has been formed into a soft mass, is then inserted into the tubular member and the tubular member is flattened to form a thin film tube. Means are provided for forming a hermetically sealed cross-seal which are disposed substantially transverse to the longitudinal forward moving direction of the web. U.S. Pat. No. 6,058,680 is incorporated herein by reference in its entirety.
Copending U.S. application Ser. No. 09/435,559 filed Nov. 8, 1999 to Kong et al discloses a multi-layer film having an improved composite structure for providing hermetic seals to packages manufactured in high speed packaging apparatus. The structure of the multi-layer film includes layers A/B/C/D. Skin layer A is formed from polypropylene copolymer with melt flow rate greater than one or linear high density polyethylene with melt index greater than one. Core layer B is formed from polypropylene. Intermediate layer C has the primary function of compliance during sealing, and sealing layer D has the primary function of providing adhesivity to the completed seal. The sealing layer D includes an antiblocking agent comprising non-distortable organic polymer particles having an average particle size greater than 6 microns. Copending U.S. application Ser. No. 09/435,559 is incorporated herein by reference in its entirety.
The present invention provides a thermoplastic multi-layer film for forming hermetic seals on packages comprising layer A comprising polyethylene, layer B comprising polypropylene, layer C comprising a copolymer, and an adhesion promoting coating applied to layer C.
The present invention provides a multi-layer film and a method of improving multi-layer films whereby hermetic seals can be simply and efficiently formed and whereby excellent seat characteristics are achieved.
The present invention includes a core layer B of oriented polypropylene. It is noted that such a polypropylene layer B alone (without additional layers) characteristically has a stiffness or modulus which prevents or significantly reduces the ability to seal the film together where the film is bent to form overlaps or fins. In one embodiment the layered film has good barrier properties and can include a metallized film layer. For example, the layered film can include one or more additional layers selected from the group consisting of oriented polypropylene, ethylene-propylene copolymers, polyethylene terephthalate, polyamide, polyacrylonitrile copolymer, polyvinylidene chloride, fluoro-polymers, ethyl-vinyl alcohol copolymers, and mixtures thereof. Other layers can be barrier resins, tie resins, metallized film, ceramic deposited film (e.g., SiO4), plasma chemical vapor deposited film, and metal, ceramic, plasma chemical vapor.
The layered film may be laminated through skin layer A to additional outer webs, such as oriented polypropylene (OPP), polyethylene terephthalate (PET), polyamide, polyethylene, and other mono- or multi-layer films. Layer A can also be metallized and then laminated, through the metal layer, to other films, such as a multi-layer biaxially oriented polypropylene film.
Layer C and the coating provide a sealing function and are bonded to layer B. These layers include a layer C, which is directly bonded to layer B, and a coating applied to the layer C.
In one embodiment, the C layer should has sufficient thickness and has sufficient flow property under sealing conditions to deform and comply with all unfilled space between the sealing jaws during sealing. The term xe2x80x9ccomplyxe2x80x9d means to be easily and inelastically forced to occupy all empty space remaining between sealing jaws while the sealing jaws are in the closed or seal position.
Polyethylene or polypropylene co- and terpolymers are contemplated for use in the layer C. The layer C material should flow under heat and pressure imposed by jaws of commercial sealing apparatus to occupy all the space between the jaws.
In another embodiment, the layer C may further comprise inorganic particles, such as solid oxides, having an average particle size greater than 2 microns. These inorganic particles of the layer C may be composed of silica (SiO2), metal carbonates (including alkali metal carbonates, such as calcium carbonate), metal silicates (including alkali metal silicates, such as magnesium silicate, and other metal silicates, such as aluminum silicate), metal phosphates (including alkali metal phosphates, such as calcium phosphate), clays, talc, diatomaceous earth, glass and the like. Examples of inorganic blocking materials include the Syloids, available from W. R. Grace Davison Division, synthetic amorphous silica gels having a composition of about 99.7% SiO2 and a particle size of about 2-4 microns, particularly Syloid 244, having a particle size of about 2.0 microns. Also useful are Super Floss, from World Minerals, a diatomaceous earth of the composition SiO2 92%, Al2O3 44%, Fe2O3 1.2%, having an average particle size of about 5.5 microns; and synthetic precipitated silicates such as Sipernat 44, available from Degussa Corporation of Akron Ohio, having a composition of SiO2 42%, Al2O3 36%, Na2O 22% and having a 3.5 micron mean particle size.
In another embodiment, the particle size of the optional inorganic particles of the antiblocking agent may be from 1 microns to 15 microns, in a second embodiment from 2 microns to 8 microns, and in a third embodiment about 4 microns. The loading of the inorganic particles in the layer C may be from 600 ppm to 5,000 ppm, in a second embodiment from 1,000 ppm to 3,000 ppm, and in a third embodiment from 1,500 ppm to 2,500 ppm.
In one embodiment, the coating can contain a component which readily forms a seal under sealing heat and pressure conditions. Such components can include polyethylene acrylic acid (LTSC) or polyvinylidene chloride (saran), and mixtures thereof.
In another embodiment, the polypropylene of layer B may be the homopolymer Fina 3371 sold by the Fina Oil Company. The polypropylene of layer B may be a homopolymer or a copolymer. Propylene homopolymers for layer B include isotactic polypropylene, in a second embodiment 80-100% isotactic polypropylene, and in a third embodiment about 95% isotactic polypropylene. In another embodiment, the propylene homopolymers may have a melt flow (measured in accordance with the standard ASTM D1238 method) ranging from about 1.2 to about 10 g/10 minutes, and in another embodiment from about 2.5 to about 6 g/10 minutes. Particular propylene copolymers include (98-93)/(2-7) propylene/ethylene copolymers.
In one embodiment, layer A comprises a linear high density polyethylene having a density of greater than 0.940 g/cc, e.g., from about 0.941 to about 0.970 g/cc. It is well known that the density of polyethylene is decreased by copolymerizing ethylene with other olefins, especially those having four or more carbon atoms. Therefore, in another embodiment, it will be understood that the linear high density polyethylenes are free or substantially free of other comonomers. It is also well known that linear high density polyethylenes can be prepared with a variety of coordination-type catalysts.
As described in U.S. Pat. No. 5,929,128 incorporated herein by reference in its entirety, linear high density polyethylene is essentially free of long chain branching.
In another embodiment, layer A comprises a medium density polyethylene having a density of from about 0.926 g/cc to about 0.940 g/cc.
In one embodiment, the polypropylene copolymer of layer C may be a copolymer of propylene with one or more olefins, such as ethylene and C4 to C10 alpha-olefins. Such polypropylene copolymers may include at least 80 mole % of propylene.
In another embodiment, the layer C thickness may be from 3 microns to 15 microns, in a second embodiment from 5 microns to 10 microns, and in a third embodiment from 7 microns to 9 microns.
In one embodiment, the coating thickness may be less than 4 microns, in a second embodiment from 0.1 microns to 3 microns, and in a third embodiment from 0.2 micron to 2 microns. In another embodiment, the coating weight is 0.1 to 5.0 gms./msi, in a second embodiment 0.6 to 0.7, or 1.5 to 2.6 gms./msi, and in a third embodiment 0.65 or 2.6 gms./msi.
In another embodiment, the layer B thickness may be from 5 microns to 25 microns, in a second embodiment from 8 microns to 20 microns, and in a third embodiment from 10 microns to 15 microns.
In one embodiment, the layer A thickness may be from 0.5 microns to 15 microns, in a second embodiment from 1 microns to 10 microns, and in a third embodiment from 3 microns to 8 microns.
In another embodiment, the multi-layer film comprising layers A, B, C, and the coating may be uni-axially or bi-axially oriented.
In another embodiment, Layer C and the coating may have a thickness of from about 15% to about 70% of the total thickness of layers A, B, and C, for example, from about 20% to about 60% of this total thickness. The thickness of the layer C may be from about 10% to about 99% of the total thickness of layer C and the coating, for example, from about 40% to about 95% of this total thickness.
The present invention provides a multi-layer film which is hermetically sealable and a method of improving the seal characteristics of multi-layer films which are hermetically sealable in high-speed packaging machines. In order to provide a hermetic seal to packages formed from multi-layer films, care must be taken to provide a sealing medium which accommodates the nature of the barrier film used for the package, i.e., its modulus or stiffness, thickness, adversity to temperature and pressure imposed under sealing conditions, etc. xe2x80x9cHermetic sealsxe2x80x9d as used herein means both peelable and unpeelable seals which provide hermetic barrier properties, i.e., does not permit passage of a gas.
As pointed out in U.S. Pat. No. 5,888,648, two separate layers may be used to provide a sealing function. Each layer is primarily designed to fulfill one of the required sealing functions, and certain imperfections in hermetic seals normally associated with high-speed film packaging can be avoided. Specifically, the outside layer (layer C) primarily meets the requirement of xe2x80x9ccompliancexe2x80x9d throughout the volume between the surfaces of sealing jaws of high-speed packaging apparatus during the sealing function. Another layer or coating (the coating), on the other hand, primarily meets the requirement of providing high performance adhesion under sealing conditions. Bearing in mind that sealing conditions include both high temperature and pressure imposed on the coating and outside layer, both the outside layer and the coating will participate in both of the sealing functions, i.e., compliance and adhesion. However, the primary function of the outside layer is to provide compliance while the primary responsibility of the coating is to provide adhesivity. Thus, the composition of the outside layer is usually different from the composition of the coating.
Since the primary function of the outside layer is compliance between the sealing jaws, the outside layer should have two attributes to fulfill its function, sufficient thickness and a flow property to comply with the space between the jaws.
xe2x80x9cCompliancexe2x80x9d in the context of the present disclosure means the ability to be easily and non-elastically deformed to fill and conform to the entire space between the sealing surfaces of a sealing jaw. Sealing jaws can operate from a temperature of from about 120xc2x0 C. to about 190xc2x0 C., and normally are imposed on a film packaging material at a pressure of from about 120 psi to about 180 psi.
Sealing jaws are illustrated and described in U.S. Pat. No. 5,888,648. Sealing jaws can be flat, or, in many cases, are provided with teeth. A complementary jaw is used in conjunction with a sealing jaw such that the teeth of the sealing jaw mesh with the valleys the complementary jaw. The surfaces of the jaws close in the sealing position on two multi-layer films, thereby clamping the films therebetween. To form a hermetic seal, the volume between the surfaces must be completely filled during sealing. These are the normal sealing conditions under which the outside layer must be capable of compliance.
The outside layer should have sufficient material to undergo compliance without leaving a void. Thus, the thickness of the outside layer should be such that a continuum of material is provided throughout the space between the surfaces of the sealing jaw. The flow property of the intermediate layer should be such that in the presence of the temperature and pressure exerted during sealing, the material maintains a viscosity which is easily deformed but maintains a non-interrupted mass throughout the space between the sealing surfaces.
In one embodiment, random copolymers of ethylene and propylene or a random terpolymer of ethylene-propylene-butylene (EPB) have been found to be excellent components for the outside layer C. These components are inexpensive and have the correct compliance requirements for layer C. These components can be used alone or in combination with other components, such as linear low density polyethylene.
In another embodiment, the coating has the primary responsibility of providing adhesivity. Thus, the components of the coating should be selected based on their ability to provide good adhesive seal strength, i.e., adequate tensile strength of the seal. Inasmuch as the primary function of the coating is that of adhesivity, the thickness of the coating is less than the thickness of the outside layer C. It has been found that polyethylene acrylic acid (LTSC) and polyvinylidene chloride (saran) are excellent for use as a component in the coating. The coating can optionally include organic and/or inorganic antiblocks to facilitate film machinability. In one embodiment, the coating is an adhesion promoting coating.
1. 1 gms./msixe2x80x94A coating thickness of 1 gram per thousand square inches
2. 1 micronsxe2x80x94A length of 1 millionth of a meter or 0.0000394 inches
3. Biaxially orientedxe2x80x94stretched in the machine direction, the direction of the feed, and in the transverse direction, perpendicular to the feed
4. Coatingxe2x80x94A layer applied to an outside surface of the film
5. Coextrudingxe2x80x94A process for producing a multi-layer film where the melted components of each layer are simultaneously fed through a die which stacks the layers on top of each other
6. Comprisingxe2x80x94Made up of at least the named components (can also include other unnamed components)
7. Copolymerxe2x80x94An elastomer produced by the simultaneous polymerization of two or more dissimilar monomers, like 90% polyethylene and 10% polypropylene
8. Corona treatingxe2x80x94A process involving an electrical discharge that causes the ionization of oxygen and the formation of ozone
9. Crimp sealxe2x80x94A join of two or more layers formed by applying heat and pressure to connect the layers
10. Elevated temperaturexe2x80x94A temperature from about 100 to about 300 degrees Fahrenheit, or from about 38 to about 150 degrees Centigrade
11. Filmxe2x80x94A thin material from about 10 to about 50 microns thick
12. Fin sealxe2x80x94A join of two or more layers formed by applying heat and pressure to connect the flaps of the layers
13. Flame treatmentxe2x80x94A process involving a flame that causes ionization of oxygen
14. Hermetic sealxe2x80x94A seal which does not permit passage of gas (such as air)
15. High density polyethylenexe2x80x94A polyethylene having a density greater than about 0.940 grams per cubic centimeter
16. Lap sealxe2x80x94A join of two or more layers formed by applying heat and pressure to connect the overlap of the layers
17. Machine directionxe2x80x94Substantially parallel to the direction of the process feed
18. Medium density polyethylenexe2x80x94A polyethylene having a density of from about 0.926 to about 0.940 grams per cubic centimeter
19. Metallizedxe2x80x94A surface that has a metal coating applied (usually aluminum)
20. Minimum Seal Temperature (MST)xe2x80x94Minimum temperature that will produce a 200 gram seal (ASTM #F-88)
21. Mixturexe2x80x94A heterogenous association of substances that can not be represented by a chemical formula. Its components can usually be separated by mechanical means
22. Orienting filmxe2x80x94Stretching film by pulling the ends in opposite directions
23. Plasma Treatmentxe2x80x94A process involving a neutral mixture of positively and negatively charged particles interacting with an electromagnetic field
24. Polyethylenexe2x80x94A thermoplastic polymer produced by polymerizing primarily ethylene monomers
25. Polyethylene acrylic acidxe2x80x94A polymer formed from the polymerization of the monomers ethylene and acrylic acid
26. Polyvinylidene chloridexe2x80x94A stereoregular thermoplastic polymer produced by polymerizing vinylidene chloride and optionally with other unsaturated compounds. Also known as xe2x80x9csaranxe2x80x9d
27. Primingxe2x80x94A process to prepare the outside surface for a coating
28. Reverse direct gravure coating processxe2x80x94A process to apply a coating wherein cells are engraved into a roll surface (gravure roll), and coating is supplied to the rotating gravure roll from a pan, filling the cells and covering the roll surface, the excess is wiped off by a doctor blade. The gravure roll operates in the opposite direction to the web, and the nip is maintained at very light contact by adjustable roll stops. The wiping action blends the dots together, yielding uniform light coatings.
29. Thermoplasticxe2x80x94A high polymer that softens when exposed to heat and returns to its original condition when cooled to room temperature
30. Thicknessxe2x80x94a caliper measurement
31. Transverse directionxe2x80x94Substantially perpindicular to the direction of the process feed
32. Uniaxially orientedxe2x80x94stretched in only one direction, either machine, in the direction of the feed, or in the transverse direction, in the direction perpendicular to the feed direction